油化学
Online ISSN : 1884-2003
ISSN-L : 0513-398X
9 巻 , 12 号
選択された号の論文の12件中1~12を表示しています
  • 高木 徹
    1960 年 9 巻 12 号 p. 633-637
    発行日: 1960/12/20
    公開日: 2009/10/09
    ジャーナル フリー
  • 福島 正敏, 下飼 勝次郎
    1960 年 9 巻 12 号 p. 638-644
    発行日: 1960/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    The Series of acyloins were prepared from C6C16 saturated fatty acid methyl esters by means of the method studied by V.L. Hansley. These acyloins were quantitatively oxidized with Wijs solution to give the corresponding α-diketones. The properties of these acyloins and α-diketones were discussed in this study.
    The melting point of each α-diketone is higher than that of the corresponding acyloin. The hydroxyl group of acyloins can be quantitatively acetylated by the acetic anhydride, and carbonyl groups of both compounds can also quantitatively react with hydroxylamine hydrochloride. Therefore these reactions may be employed to analytical procedure, including determination of hydroxyl and carbonyl groups. The 2, 4-dinitrophenyl hydrazones (DNP) of both compounds were prepared by the standard method. The melting points and N-contents of corresponding DNP were very close and ultraviolet absorption spectroscopy which indicates the electronic transition in the DNP molecule was perfectly agreed together. It came to conclution that DNP of acyloins are identical with DNP of α-diketones.
    In glacial acetic acid solution vicinal functional groups of both compounds were quantitatively oxidized by periodic acid. On the other hand the reaction with periodic acid in the 99% ethanol solution was different in the case of acyloins and α-diketones. Namely, α-diketones cannot be oxidized, though acyloins can be easily done. It is possible to determine the acyloins in the presence of the α-diketones by nonaquous acid-base titration of formed fatty acids.
    The infrared spectroscopy of both compounds was discussed.
  • 永野 義彰, 田中 武英
    1960 年 9 巻 12 号 p. 645-649
    発行日: 1960/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    Following to the previous reports in which the qualitative investigation on the thermal isomerization of methyl linoleate and methyl linolenate was carried out, the quantitative investigation was discussed in this paper. At first, pure isomers were prepared by following methods.
    Cis-isolated isomer was prepared by combining the urea complex method and the low temperature crystallization as previously reported. Cis-trans conjugated one was prepared by the alkali-isomerization of cis-isolated and then purified by the low temperature crystallization. Trans-isolated one was prepared by the isomerization of cis-isolated with selenium, and then purified by vacuum distillation and low temperature crystallization.
    Trans-trans conjugated one which is obtainable from castor oil as “von Mikusch Acid”, was prepared by the thermal isomerization of cis-trans conjugated and then purified by vacuum distillation and low temperature crystallization. The infrared absorption characteristics of these pure isomers were determined and the quantitative investigation on the thermal isomerization of methyl linoleate and methyl linolenate was carried out.
  • 福住 一雄
    1960 年 9 巻 12 号 p. 649-652
    発行日: 1960/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    Cottonseed oil, methyl oleate and methyl linoleate were oxidized at various temperatures ranging between 0 and 180°C for 24hr with aeration. They were then treated with egg albumin in an aqueous medium under the atmosphere of nitrogen at 60±2°C for 2hr with agitation at the rate of about 250rpm. The lipid-protein complexes and unreacted lipid fractions were isolated and such lipid fractions were compared with the oxidized lipids originally used.
    It was confirmed that only the lipid materials which had been oxidized to a sufficient degree formed complexes with protein. In all cases, however, the maximum level of lipids contained in the complexes was considerably limited : utmost 1.3%, 0.3%, and 0.3% on a weight basis, for oxidized cottonseed oil, methyl oleate and methyl linoleate, respectively. The refractive indices, viscosities, iodine values and peroxide values were failed to give information on the possible mechanism of the complex formation.
    The amounts of lipids contained in the complexes are approximately constant when the lipid-protein complexes are formed with cottonseed oil, methyl oleate and methyl linoleate oxidized at or above 90, 120, 30°C, respectively. But in the complex formed with methyl linoleate oxidized at 180°C, this value is small. Total trans isomers contents in oxidized cottonseed oil, methyl oleate and methyl linoleate are approximately constant when the lipids are oxidized at or above 90, 120 and 60°C, respectively. But in methyl linoleate oxidized at 180°C, this value is small. These facts show that there is an intimate relationship between total traps isomers produced in thermal oxidation of lipids and lipid-protein complex formation.
  • 荻野 圭三
    1960 年 9 巻 12 号 p. 653-657
    発行日: 1960/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    The phase transition of crystalline form of typical sodium soaps, ranging from sodium laurate (C12) to sodium stearate (C18), were studied by the measurement of change in the specific heat. It is known from the previous X-ray diffraction studies that sodium soap molecules align parallel to the long axes of their hydrocarbon chain and the ionic ends are adjacent to each other, thus they form the bimolecular laminate. By using the above-mentioned model, the relation of the van der Waals' force acting between the adjacent hydrocarbon chains and the Coulomb force acting between the ionic layers or adjacent molecules is clarified. From this, it is shown that the balance of two sorts of forces acting between two molecules is altered by the length of paraffinic carbon chain. In sodium laurate, Coulomb force acting between the adjacent hydrocarbon chains is strongnger than van der Waals' force acting between the ionic ends of the adjacent layer, and then the behavior of phase transition of sodium laurate is similar to the ionic crystal. In the myristate and palmitate, the balance between the two forces is kept generally and they show the similar behavior in the change of phase transition. In sodium stearate, the thermal behavior is different from other soaps because of that the thermal motion is complicated.
  • 桜井 洸, 岡本 能樹
    1960 年 9 巻 12 号 p. 658-661
    発行日: 1960/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    The synthesis of sodium alkylphosphonate from fatty acid ester of higher alcohol or paraffin wax with phosphorus trichloride and oxygen gas was investigated. The phosphorus content of the reaction product in both cases using the ester and paraffin wax, increased proportionally with the volume of oxygen gas at the condition of constant flow speed of the gas and in the presence of sufficient amount of phosphorus trichloride. The reaction process was almost unaffected by the temperature between 25° and 60°C. The proceeding of this reaction was completely interrupted by adding small amount of iodine. The sodium phosphonates prepared from the ester or spermaceti could be used as a good antistatic agent for synthesized fibers, such as nylon, vinylon, tetolon and etc., however, the derivatives of paraffin wax had not such properties.
  • 1960 年 9 巻 12 号 p. 661a
    発行日: 1960年
    公開日: 2009/10/09
    ジャーナル フリー
  • 1960 年 9 巻 12 号 p. 661b
    発行日: 1960年
    公開日: 2009/10/09
    ジャーナル フリー
  • 1960 年 9 巻 12 号 p. 661c
    発行日: 1960年
    公開日: 2009/10/09
    ジャーナル フリー
  • 古賀 雄造
    1960 年 9 巻 12 号 p. 662-664
    発行日: 1960/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    There are several kinds of urea dewaxing process applicable to petroleum fractions. If the recovery of urea from adducts could be simplified, the dewaxing process by solid urea is interesting. Thus, we investigated the solvent extraction of component hydrocarbons from adducts to decide whether this technique is effective or not for applying the continuous dewaxing operation.
    Toluene was used as the extracting solvent, and extracted at 95°C. Then, we re-used the recovered urea to form urea adduct. The extracting efficiency was not satisfactory. Furthermore, hydrocarbons which have stronger affinity to urea were gradually accumulated. Consequently, subsequent urea adduction was gradually reduced, and inhibitive substances were gradually accumulated in both of recovered solvent and urea.
    With the experimental results, we understand that this process is not suitable.
  • 横溝 清治, 林 雅博
    1960 年 9 巻 12 号 p. 664-668
    発行日: 1960/12/20
    公開日: 2009/10/09
    ジャーナル フリー
  • 1960 年 9 巻 12 号 p. 669-671
    発行日: 1960/12/20
    公開日: 2009/10/09
    ジャーナル フリー
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